Method of protecting plants against insects with mixed esters



United States Patent METHOD OF PROTECTING PLANTS AGAINST INSECTS WITH MIXED ESTERS Winchester L. Hubbard, Woodbridge, Allen E. Smith, 0x-

ford, and Rupert A. Covey, Wolcott, Conn., assignors to United States Rubber Company, New York, N.Y., a

corporation of New Jersey No Drawing. Original application Aug. 20, 1962, Ser.

No. 218,093, now Patent No. 3,179,683, dated Apr. 20,

1965. Divided and this application Aug. 7, 1964, Ser.

18 Claims. (Cl. 167-30) This application is a division of our application Serial No. 218,093, filed August 20, 1962, now US. Patent 3,179,683, issued April 20, 1965 which is a continuationin-part of our application Serial No. 131,743, filed August 16, 1961, now abandoned.

This invention relates to new chemicals, namely new organic esters of sulfurous acid, more particularly to mixed sulfite esters of phenols and glycol ethers.

The new compounds of the present inevntion are useful as insecticides, particularly for the control of mites. They may also be used as plasticizers.

The chemicals of the present invention may be represented by the general formula f ll in which R and R are aromatic radicals, e.g. phenyl, or naphthyl, or a phenyl or napthyl (aryl) radical having one or more substituents in the aryl nucleus selected from the group consisting of alkyl, cycloalkyl, haloalkyl, alkoxy and halo; n is 2 to 10, and m is 1 to 10. Where m is greater than 1, the repeating oxyalkyl groups may be the same or different. Examples of R and R are phenyl, 1- naphthyl, Z-naphthyl, p-tolyl, o-tolyl, isopropylphenyl, tert.-butylphenyl, tert.-amylphenyl, nonyl-phenyl, cyclohexylphenyl, chloromethylphenyl, methoxyphenyl, bromophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, trichlorophenyl, pentachlorophenyl. Examples of the -OC,,H group are ethyleneoxy, trimethyleneoxy, tetramethyleneoxy, propyleneoxy, l,2-dimethylethyleneoxy.

The preparation of the chemicals of the invention may be carried out by reacting the selected phenol with the separately prepared chlorosulfinate of the selected glycol ether, which may be made by reacting the selected glycol ether with thionyl chloride. The glycol ether which is a glycol monoether may be made by reacting the selected phenol, with one to ten moles of the selected alkylene oxide per mole of the phenol. Such preparation is illustrated by the following reactions with the same symbols R, R and m as in the above general formula and for convenience using ethylene oxide (11:2) as the alkylene oxide:

001120112) OH soon m 3,291,685 Patented Dec. 13, 1966 containing one alkylene oxide unit. With two or more moles of alkylene oxide per mole of phenol, a mixture of products having varying numbers of alkylene oxide units is produced. If a compound with a specific number of alkylene oxide units is desired, the mixture may be fractionated. In the present invention for insecticidal uses, it is satisfactory to have mixtures of compounds containing different numbers of alkylene oxide units from 1 to 10. The following reaction of p-te-rt.-butyl phenol with propylene oxide is illustrative of the well known preparation of the starting glycol ethers according to reaction (1) above:

p-Tert.-butyl phenol (300 g., 2.0 moles) and 4 g. sodium hydroxide were combined and the mixture heated to 150 C. Propylene oxide (279 ml., 232 g., 4.0 moles) was added during two hours maintaining the reaction temperature at ISO-160 C. The mixture was cooled, the catalyst was neutralized with dilute hydrochloric acid, and the product taken up in benzene. The benzene was removed and the product heated to C. (0.5 mm.) to remove the last traces of volatile materials. The crude reaction mixture weighed 509 g. (95.7%). It was a mixture of compounds having the structure where m=1, 2, 3, 4, 5, etc. The mixture was distilled and the following fractions collected:

Center cuts of these fractions yielded the pure compounds as follows:

m=1, B.P.116 C. (1 mm.) m=2, B.P.1461S3 C. (1 mm.) m=3, B.P.175 177" C. (1 mm.)

The preparation of the chlorosulfinates of the glycol ethers according to reaction (2) is carried out at a temperature of between 5 C. and 30 C., preferably near 0 C., and the yield of chlorosulfinate is nearly quantitative. An inert solvent such as benzene, xylene or solvent naphtha may be used. This is illustrated in Example I below.

The preparation of the sulfite esters is carried out in the presence of an HCl acceptor, such as pyridine, dimethyl aniline or trimethylamine, and in a solvent such as benzene, xylene or solvent naphtha. The reaction temperature is generally between l0 C. and 50 C., prefera'bly near 0 C. This is illustrated in Example I rbelow. Examples of the sulfite diesters of the presentinvention are:

Phenyl phenoxyethyl sulfite Phenyl o-toloxyethyl sulfite Phenyl m-(n-propyDphenoxyethyl sulfite Phenyl p-isopropylphenoxyethyl sulfite Phenyl p-tert.-amylphenoxyethyl sulfite Phenyl p-chlonophenoxyethyl sulfite Phenyl p-tert.-butylphenoxyisopnopyl sulfite Nonylphenyl p-tert.-butylphenoxyisopropyl sulfite Phenyl o-tertAbutylphenoxyethoxyisopropyl sulfite p-Cyclohexylphenyl o-toloxyethyl sulfite p-Chloromethylphenyl p-tert. butylphenoxyisopropyl sulfite n-Methoxyphenyl p-tert. butylphenoxyisopropoxyisopropyl sulfite o-Tolyl |pcyclohexylphenoxyisopropy-l sulfite Phenyl p-toloxyoctyl sulfite l-naphthyl p-chloromethylphenoxyethyl sulfite l-naphthyl lp-methoxyphenoxyethoxyethyl sulfite l-naphthyl p-terL-bu-ty'lphenoxyisopropoxyisopropyl sulfite o-Tolyl o toloxyisopropyl sulfite o-Tolyl o-toloxyethylpropyl sulfite o-Tolyl phenoxyisopropyl sulfite o-Tolyl p-isopropylphenoxyethyl sulfite o-Tolyl l-orthotoloxy-Z-butyl sulfite o-Tolyl p-isopropylphenoxyisopropyl sulfite m-Tolyl p-terL-butylphenoxyisopropyl sulfite o-Tolyl o-chlorophenoxytriethoxyethyl sulfite o-Tolyl p-tert.-butylphenoxyisopropyl sulfite o-Tolyl p-tert.ebutylphenoxyisopropoxyisopropyl sulfite m-Chlorophenyl o-isopropylphenoxyhexoxyhexyl sulfite o-Tolyl 1-paraisopropylphenoxy-Z-butyl sulfite o-Tolyl 1-paratert.-butylphenoxy-Z-butyl sulfite o-Tolyl 1-paratert.-amylphenoxy-2-butyl sulfite o-Tolyl 3-paratert.-butylphenoxy-2 butyl sulfite o-Tolyl 1-paratert.-butylphenoxy-2-amyl sulfite Example I illustrates the preparation of the compounds of the present invention.

EXAMPLE I Preparation of 0401 1 p-tert.-butylpkenoxyisopropyl sulfite p-Tert.-butylphenoxyisopnopyl chlorosulfinate was prepared as illustrated in reaction (2) above as follows: p-tert. butylphenoxyisopropyl alcohol or propylene glycol mono-p-tertsbutylphenyl' ether (104 .g., 0.5 mole) prepared according to reaction (1) as described above was dissolved in 150 ml. benzene and the solution was cooled to C. C. Thionyl chloride (45.4 ml., 74.4 g., 0.625 mole) was added dropwise during one hour, maintaining the reaction temperature 'below 5 C. The mixture was allowed to warm to room temperature and stand for hours. The benzene was evaporated under reduced pressure at room temperature and the residue was warmed to 35 C. (0.8 mm.) to remove the last traces of solvent. Yield, 141.3 g. (97.3%) of a pale yellow oilwhich was nearly odorless and relatively stable when stored in a refrigerator.

The o-tolyl p-tert.-butylphenoxyisopropyl sulfite was prepared as illustrated in reaction (3) above as follows: o-cresol (5.9 g, 0.055 mole), 4.1 ml. (4.0 g, 0.05 mole) pyridine and30 ml. xylene were combined and the solution cooled 000 C.-5 C. A solution of 14.5 g. (0.05 mole) p-tert.abutylphenoxyisopropyl chlorosulfinate in 10 ml. xylene was added during min. 'keeping the reaction temperature below 5 C. The mixture was stirred for 1 hour and was washed twice with ml. portions of water. The mixture was then stirred for one hour with 50 ml. 2 N NaOH. The two layers were separated and the xylene layer was washed several times with saturated salt solution until the washings were neutral to pH paper. The xylene was removed under reduced pressure and the residue heated to a pot temperature of 135 C. (0.7 mm). The product was filtered through Dicalite (a diatomaoeous earth filter-aid) giving 13.9 g. (77% yield) of a reddish yellow oil.

Analysis.Calculated for C H O S: C, 66.26%; H, 7.23%; S, 8.85%. Found: C, 67.44%; H, 7.68%; S, 8.13%.

Sulfur analyses of other vention were:

Nonphenyl p-tert. butylphenoxyisopropyl sulfite. Calculated S, 6.75%. Found: 6.77%.

p-Tert.-butylphenyl p-tert.-amylphenoxyethyl sulfite. Calculated S, 7.92%. Found: 7.36%.

o-Folyl p-tert.-arnylphenoxyethyl sulfite. Calculated S, 8.85%. Found: 8.31%.

o-Tolyl oatoloxyisopropyl sulfite. 10.01%. Found: 9.80%.

o-Tolyl o-toloxyethyl sulfite. Calculated S, 11.05%. Found: 10.29%.

chemicals of the present in- Calculated S,

' baskets under greenhouse Phenyl p-isopropylphenoxyethyl sulfite. Calculated S, 9.99%. Found: 9.65%.

o-Tolyl phenoxyisopropyl sulfite. 10.48%. Found: 9.91%.

o-Tolyl p-isoprop-ylphenoxyethyl sulfite. Calculated S, 9.59%. Found: 9.08%.

o-Tolyl l-orthotoloxy-Z-butyl sulfite. 9.59%. Found: 9.17%.

o-Tolyl p-isopropylphenoxyisopropyl sulfite. la-ted S, 9.20%. Found: 8.51%.

o-Tolyl 1aparaisopropylphenoxy-Z- butyl sulfite. Calculated S, 8.85 0. Found 8.04%.

o-Tolyl 1paratertiaryamylphenoxy-Lbutyl sulfite. Calculated S, 8.20%. Found: 7.38%.

-o-Tolyl 3paratertiarybutylphenoxy-2 butyl sulfite. Calculated S, 8.52%. Found: 8.37%.

o-Tolyl 1-paratertiaryhutylphenoxy-Z-amyl sulfite. Ca1- culated S, 8.33%. Found 7.55%.

EXAMPLE II This example illustrates the insecticidal activity of the chemicals of the present invention in tests against the larvae of Aedes aegypti (L) mosquitoes. Fourth instar larvae were used. These larvae normally reach this stage in 5 days at F. after hatching.

To 10 mgs. of each chemical to be tested was added 1 ml. of acetone and ml. of water to give a concentration of 100 parts per million (p.p.m.).

Twenty-five ml. aliquots, replicated once, of each chemical to he tested at concentrations of 100 p.p.m. and of checks Without the chemical and of plain water checks were placed in test tubes and from 5 to 25 larvae were added. The tubes were held at 70 F. in darkness for 72 hours. At the end of this period the live and dead larvae were counted and the percent mortality calculated. All the larvae were alive in the checks (0% mortality). The percent mortality of the larvae treated with the chemicals of the present invention is shown in the following table:

Chemical: Percent mortality o-Tolyl p-tert.-'butylphenoxyisopropyl sulfite 100 Nonylphenyl p-tert.abutylphenoxyisopropyl sul- Calculated S,

Calculated S,

Calcu- EXAMPLE In This example illustrates the elfectiveness of the chem icals of the present invention for controlling mites.

Pinto beans in the two-leaf stage and grown in 4" conditions at 70 F.75 F. were used. Three plants for a total of six leaves were in each basket for each test. The tests on the chemicals and checks face-active dispersing agent (isooctylphenyl polyethoxy ethanol). and 1 ml. of acetone, washing into 200 ml. of water, agitating to form a dispersion and diluting with water to the desired concentrations of 1000 p.p.m. and 200 p.p.m.

. The sprayings thoroughly Wet the upper surface of the leaves. The plants were returned to the greenhouse. The following day (20-24 hours later), rings of an adhesive preparation non-toxic to the organisms under test, such as is Mites were transferred to the thus treated leaves by placing bean A count of the number of mites transferred was made the Percent control: 100 1 F1nal count living mltes) Original count The control of mites by the chemicals of the present invention at the various concentrations is shown in the following table (the check treatments without the chemicals had about 20% mortality):

Percent Control at- Chemicals 1,000 p.p.m. 200 p.p.m.

O-Tolyl p-tert butylphenoxyisopropyl sulfite 100 92 Nonylphenyl p-tert.-butylphenoxyisopropropyl sulfite 59 p-Tert.-butylphenyl p-tert.-amylphenoxyethyl sulfite 99 82 oTolyl p-tert.-arnylphenoxyethyl sulfite 100 95 o-Tolyl o-tolyloxyisopropyl sulfite 100 79 o-Tolyl o-tolyloxyethyl sulfite 96 96 Phenyl p-isopropylphenoxyethyl sulfite. 94 71 o-Tolyl phenoxyisopropyl sulfite 80 75 o-Tolyl p-isopropylphenoxyethyl sulfite. 99 66 o-Tolyl l-orthotoloxy-Z-butyl sulfite 99 95 o-Tolyl p-isopropylphenoxy-isopropyl sulfite 99 93 m-Tolyl p-tert.-butylphenoxyisopropyl sulfite 91 90 O-Tolyl l-paraisopropylphenoxy-Z-butyl sutfite 97 76 o-Tolyl 1 parateritarybutylphenoxy-2- butyl sulfite 100 99 o-Tolyl l-paratertiaryamylphenoxy-2- butyl sulfite 98 97 o-Tolyl 3-paratertiarybutylphenoxy-zbutyl sulfite 100 97 o-Tolyl l-paratert ybutylphenoxy-2- amyl sultite 100 95 o-Tolyl p-tert.-butylphenxy1sopropoxyisopropyl sulfite 92 84 EXAMPLE IV This example also illustrates the effectiveness of the chemicals of the present invention for controlling mites.

Pinto beans in the two-leaf stage and grown in 4" baskets under greenhouse conditions at 70 F.-75 F. were used. Two plants for a total of four leaves were in each basket for each test. These tests on the chemicals were replicated once.

The untreated leaves were ringed with adhesive and 40 50 mites were transferred to each leaf similarly to Example III.

The plants were then sprayed to thoroughly wet the upper surface of the leaves with aqueous solutions of the chemicals at concentrations of 200 ppm, 100 ppm. and 50 ppm. prepared as in Example III.

The plants were allowed to dry and a count of the mites was made. The plants were kept in the greenhouse for three days. A final count of the living mites remaining on the leaves was then made. The percent control is found by the formula used in Example III.

The control of mites by the chemicals of the present invention is shown in the following table:

Percent Control at Chemical 200 ppm. 100 ppm. 50 ppm.

Phenyl p-tert.-butylphenoxyisopropyl sulfite 88 93 88 o-Tolyl p-terti-amylphenoxyethyl sulfite 96 96 75 o-Tolyl p-tert.-butylphe11oxyisopropyl sulfite 90 83 81 The chemicals of the present invention may be applied in various manners for the control of insects. They may be applied to loci to be protected against insects as dusts when admixed with or adsorbed on powdered solid carriers, such as the various mineral silicates, e.g. mica, talc, pyrophillite and clays, or as liquids or sprays when in a liquid carrier, as in solution in a suitable solvent, such as acetone, benzene or kerosene, or dispersed in a suitable non-solvent medium, for example, water. In protecting plants (the term including plant parts) which are subject to attack by insects, the chemicals of the present invention are preferably applied as aqueous emulsions containing a surface-active dispersing agent, which may be an anionic, non-ionic or cationic surface-active agent. Such surface-active agents are well known and reference is made to US. Patent No. 2,547,724, columns 3 and 4 for detailed examples of the same. The chemicals of the invention may be \mixed with such surface-active dispersing agents, with or without an organic solvent as insecticidal concentrates for subsequent addition of water to make aqueous suspensions of the chemicals of the desired concentration. The chemicals of the invention may be admixed with powdered solid carriers, such as mineral silicates together with 'a surface-active dispersing agent so that a wettable powder may be obtained, which may be applied directly to loci to be protected against insects, or which may be shaken up with water to form a suspension of the chemical (and powdered solid carrier) in water for application in that form. The chemicals of the present invention may be applied to loci to be protected against insects by the aerosol method. Solutions for the aerosol treatment may be prepared by dissolving the chemical directly in the aerosol carrier which is liquid under pressure but which is a gas at ordinary temperature (e.g. 20 C.) and atmospheric pressure, or the aerosol solution may be prepared by first dissolving the chemical in a less volatile solvent and then admixing such solvent with the highly volatile liquid aerosol carrier. The chemicals may be used admixed with carriers that are active of themselves, for example, other insecticides, fungicides or bactericides.

Having thus described our invention, what we claim and desire to protect by Letters Patent is:

1. The method of protecting plants which comprises applying to the plants a chemical represented by the formula in which R and R are selected from the group consisting of aryl, alkaryl, cycloalkylaryl, haloalkylaryl, alkoxyaryl, and 'haloaryl radicals, n is 2 to 10, and m is l to 10, said aryl and substituted aryl groups being phenyl or naphthyl.

2. The method of protecting plants which comprises aplpflying to the plants o-tolyl p-tert.-butylphenoxyisopropyl su te.

3. The method of protecting plants against attack by insects which comprises applying to the plants o-tolyl otolyloxyethyl sulfite.

4. The method of protecting plants which comprises applying to the plants p-tert.-butylphenyl p-tert.-amyl phenoxyethyl sulfite.

5. The method of protecting plants by insects which comprises applying to the plants o-tolyl l-paratertiarybutylphenoxy-2-butyl sulfite.

6. The method of protecting plants which comprises applying to the plants o-tolyl 3-paratertiarybutylphenoxy- Z-butyl sulfite.

7. The method of controlling insects which comprises applying to a locus to be protected against insects a chemical represented by the formula applying to a locus to be in which R and R 8. The method of controlling insects which comprises applying to a locus to be protected against insects o-tolyl p-terL-butylphenoxyisopropyl sulfite.

9. The method of controlling insects which comprises applying to a locus to be protected against insects o-tolyl o-tolyloxyethyl sulfite.

10. The method of controlling insects which comprises protected against insects p-tert.- 'butylphenyl p-tert.-amylphenoxyethyl sulfite.

11. The method of controlling insects which comprises applying to a locus to be protected against insects o-tolyl 1-parateriarybutylphenoxy-2 butyl sulfite.

12. The method of controlling insects which comprises applying to a locus to be protected against insects o-tolyl 3-paratertiarybutylphenoxy-Z-butyl sulfite.

13. The method of combatting mites which comprises contacting mites with a chemical represented by the formula are selected from the group consisting of aryl, alkaryl, cyc'loalkylaryl, haloalkylaryl, alkoxyalkylaryl and haloaryl radicals, n is 2 to l0, and m is 1 to 10,

8 said aryl and substituted aryl naphthyl.

14. The method of combatting mites which comprises contacting mites with o-tolyl p-tert.-butylphenoxyisopropyl sulfite.

15. The method of combatting mites which comprises contacting mites with o-tolyl o-tolyloxy sulfite.

16. The method of combatting mites which comprises contacting mites with p-tert.-butylphenyl p-tert.-amylphenoxyethyl sulfite.

17. The method of combatting mites which comprises contacting mites with o-tolyl 1-paratertiarybutylphenoxy- 2-butyl sulfite.

18. The method of combatting mites which comprises contacting mites with o-tolyl 3-paratertiarybutylphenoxy- 2-butyl sulfite.

groups being phenyl or References Cited by the Examiner UNITED STATES PATENTS 2,820,808 1/1958 Harris 260-456 2,867,564 1/1959 Richter 260-456 X 2,901,338 8/1959 Richter 260456 X SAM ROSEN, Primary Examiner. G. A. MENTIS, Assistant Examiner. 

1. THE METHOD OF PROTECTING PLANTS WHICH COMPRISES APPLYING TO THE PLANTS A CHEMICAL REPRESENTED BY THE FORMULA 